CN1155293A - Oil-soluble dispersant additives based on 1-butene-alpha-olefin copolymers - Google Patents

Abstract

Oil-soluble dispersant additives are disclosed. The additives comprise the reaction product of a functionalized 1-butene copolymer and at least one nucleophilic reactant selected from amines, amino alcohols, alcohols, and reactive metal compounds. The functionalized copolymer has within its structure at least one acyl functional group selected from the group consisting of C4 to C10 dicarboxylic acids and derivatives thereof and C3 to C10 monocarboxylic acids and derivatives thereof. The 1-butene copolymer is derived from 1-butene and at least one other alpha -olefin of formula CH2=CHR', wherein R' is methyl or a C3 to C12 linear or branched alkyl group. The copolymer has a number average molecular weight of at least about 700, a molecular weight distribution of less than 5, and ethenylidene groups terminating at least about 30% of all polymer chains. The dispersant additives are useful in oleaginous compositions including lubricating oil compositions and concentrates and fuel compositions.

Description

Oil-soluble dispersant additive based on 1-butylene-alpha-olefin copolymer

The present invention relates to can be used for the oil-soluble dispersant additive in the oily composition, said composition comprises lubricating oil composition and fuel composition.The invention still further relates to the enriched material that contains dispersant additives.

Hydrocarbon oil composition generally comprises the mixture of oil and one or more additives at the bottom of at least a alkyl, and wherein each additive is used for improving performance and the character of substrate oil in its intended purpose; Purposes for example is, as lubricating oil, and heated oil, diesel oil, intermediate distillate fuel oil, or the like.Lubricating oil composition faces quite strict viscosity requirement, for example the requirement of being stipulated by SAE.This based composition must satisfy that MV minium viscosity under the high temperature (at least about 100 ℃) requires and low temperature (-5 ℃ to-30 ℃ of pacts) under high viscosity requirement.It is to arrive certain a bit in order to prevent that oil is thinning in the machine operation process that MV minium viscosity at high temperature requires, and naming a person for a particular job at this causes wear and tear in machines and increase oil consumption.High viscosity at low temperatures requires to help engine and starts at the weather of cold, but and guarantee that cold oil has enough pumps to take out ability and flowability, to avoid answering the not enough engine damage that is caused of lubrication.

In general simple mixtures with substrate oil of different viscosity characteristic can not satisfy the low and high temperature viscosity requirement of multigrade lubricating oil.The major measure that satisfies this requirement is to use viscosity modifier, is also referred to as viscosity index improver or V.I. improving agent.

Viscosity modifier generally is an oil-soluble polymers, normally has number-average molecular weight and be about 20,000 to 200,000 the polymkeric substance based on hydrocarbon.These polymkeric substance have bigger size, even can significantly improve the kinematic viscosity of substrate oil under low concentration.Yet the lubricant oil solution that contains these viscosity modifiers is a non-Newtonianism in nature.As a result, these solution trend towards having in high shear environment than the lower viscosity of the viscosity of estimating.This behavior it is believed that it is that the arrangement brought out by the shearing of V.I. polymer chain is kinetic.Thereby when operating internal-combustion engines, viscosity modifier makes the low temperature of lubricated substrate oil, the degree that high-shear (CCS) viscosity improves be lower than the degree that they improve high temperature viscosity.The amount of the viscosity modifier that required MV minium viscosity is added under for the high temperature that obtains multi-grade oil has been got rid of when satisfying under the low temperature required the most full-bodied possibility, then can reach a bit.Therefore, restricted to the amount of viscosity modifier, this viscosity modifier is used for satisfying the low and high temperature viscosity requirement of lubricating oil composition.

Lubricating oil composition generally also contains the polymer dispersed agent addition agent, and its main effect is that the insolubles that will be formed by oxidation remains in the suspension of oil, thereby avoids sludge flocculation and precipitation.Dispersion agent generally is to have number-average molecular weight " Mn " to be hydrocarbon polymer about 10,000 or 10,000 below, and this polymkeric substance contains polar group after the chemical mode modification, for example nitrogenous and the group that contains ester.The consumption of dispersion agent is subjected to the constraint and the control of the efficient of concrete material when obtaining its dissemination.The engine oil of buying in each service station of the U.S. generally contains the about 2-4 dispersion agent doubly that is equivalent to viscosity modifier, based on activeconstituents.

Common dispersion agent can be improved the low temperature and the high temperature viscosity characteristic of substrate oil by their polymer property.Yet because the size of polymer dispersant molecule is little more than the size of viscosity modifier, dispersion agent is not too responsive to shearing.As a result, with viscosity modifier Comparatively speaking, dispersion agent is bigger to the contribution of high temperature viscosity than it to the contribution of the low temperature viscosity of lubricating oil.And, on absolute sense, to compare with viscosity modifier, the dispersion agent with low polymerization degree is low to the contribution of the high temperature viscosity of substrate oil.Therefore, the low temperature viscosity that is caused by dispersion agent improves degree and can surpass the low temperature viscosity that is caused by viscosity modifier and improve degree, and and from the high temperature viscosity that viscosity modifier obtained does not improve the same benefit that is able to correspondingly improve a lot on high temperature viscosity.So, because improving, the low temperature viscosity that dispersion agent causes causes that oily low temperature viscosity approaches the highest low temperature viscosity that is allowed, thereby be difficult in a certain amount of viscosity modifier of introducing under the situation that does not surmount the low temperature viscosity threshold value, and this amount is enough to satisfy MV minium viscosity at high temperature.

Further demand is the improved dispersion agent of exploitation, and it can make lubricating oil composition that the benefit of viscosity aspect is arranged and obtain to be equal to or to surpass the dissemination of common dispersion agent simultaneously.

Be suitable for the various oil solubles, open in the prior art of lubricating oil composition based on the dispersant additives of hydrocarbon polymer.For example EP-A-208560 disclose by amine, alcohol, amido pure and mild they mixture and the formed dispersant additives of reaction of the dicarboxylic acid material that replaces of polyolefine.The dicarboxylic acid material that polyolefine replaces is to be 1500 to 5 by Mn, the prepared in reaction of 000 polyolefine (for example polyisobutene) and unsaturated dicarboxylic acid reactant (maleic anhydride), require the dicarboxylic acid that polymer product (polyisobutenyl succinic anhydride) contains the 1.05-1.25 mole to produce part/every mole of employed polyolefine in reaction.Suitable polyolefine comprises C ₂-C ₁₀The homopolymer of monoolefine and multipolymer.

US-A-5 has told about a kind of slip additive in 229,022, it comprise the end coverlet-or dicarboxylic acid produce the ethene-alpha-olefin copolymer that part replaces.The polymkeric substance that acid replaces can further react with nucleophilic reagent such as amine, alcohols and metallic compound, obtains can be used as other material of additive such as dispersion agent.

EP-A-490454 has told about the alkenyl succinimide derivative that can be used as dispersant additives, and wherein undersaturated atactic polypropylene oligopolymer obtains alkenyl from the end.Succinimide derivatives is by amber acidifying oligopolymer and C ₁-C ₅₀The reaction of amine forms.

Polyisobutene (" PIB ") is selected polymkeric substance in the polymeric dispersant normally, and is main because it is obtained by the cationic polymerization of butene stream easily.PIB is amorphous material basically, and it generally contains remaining unsaturated position, and the amount of unsaturated position is: at the nearly olefinic double bond of each polymer chain.Two keys are as making the functionalized position of PIB, for example by reacting functionalized with unsaturated carboxylic acid compounds such as maleic anhydride.

As already pointed out, ethene-alpha-olefin copolymer and alpha-olefin homo and multipolymer also once were disclosed and can be used for polymeric dispersant.By using common Ziegler-Natta (Z-N) catalyzer to carry out the skeleton that in general the prepared polymkeric substance of polyreaction is not suitable for use in the lubricating oil dispersant additive by corresponding monomer.Common Ziegler-Natta catalyst has higher activity and the reactive site of several types is arranged, obtain having Mn 10,000 or more with the alpha-olefinic polymer with wider molecular weight distribution (" MWD ").By using molecular weight regulator such as hydrogen, can obtain low-molecular-weight polymkeric substance with these catalyzer, but this can make the two keys in the polymkeric substance saturated, damaged the reactive behavior of polymkeric substance in can be used to produce the functionalized chemical reaction of dispersion agent, this activity depends on high double bond content, for example carries out functionalized with unsaturated carboxylic acid compounds such as maleic anhydride.

Ethene-alpha-olefin copolymer in the dispersant molecule weight range and alpha-olefin homo and multipolymer can be by using the catalyzer of being made up of Metallocenic compound (transistion metal compound that promptly contains cyclopentadienyl) and suitable activator or promotor such as aikyiaiurnirsoxan beta, undertaken by corresponding monomer that polyreaction prepares.For example, the US-A-5 of Zhu Minging above, 229,022 have described the purposes of metallocenes when the preparation ethene-alpha-olefin copolymer.JP-A-63/057615 discloses in the presence of the catalyzer that is formed by cyclopentadienyl zircoium hydride compound and aikyiaiurnirsoxan beta, by C ₃-C ₂₀The liquid alpha-olefin random copolymers of the copolyreaction preparation of alpha-olefin.Multipolymer has a kind of the deriving in those monomers from be present in multipolymer of 1-99 mole % and the unit that comes, and logarithmic specific concentration viscosity is 0.005-4dl/g, and MWD is no more than 3, iodine number be 0-85 and ¹³The bright multipolymer of C-NMR stave has the head-stern construction of rule.According to disclosure, this multipolymer contains unsaturated position, end at an end of copolymer chain.Embodiment 4 has described the butene content that 15 moles of % are arranged, and limiting viscosity is 0.02dl/g, MWD be 1.82 and iodine number be the preparation method of 1-butylene-1-hexene copolymer of 51.

JP-A-63/037102 has disclosed by unsaturated C ₃-C ₁₀Carboxylic acid, acid anhydrides or their ester bond are connected to alpha-olefin homo or the formed modified liquid alpha-olefinic polymer of multipolymer, this homopolymer or multipolymer be by use zirconium luxuriant-the alumoxane catalyst system is by one or more C ₃-C ₂₀Alpha-olefin carries out the polyreaction preparation.The polymkeric substance of this modification especially can be used as lubricated oil additives.According to disclosure, the limiting viscosity of starting polymer is 0.005-0.4dl/g, and Mn is 300-8,000, MWD be below 3 or 3 and ¹³The bright head of C-NMR stave-tail keyed jointing, and the triple body marks of isotactic mm are below 0.35 or 0.35.Embodiment 4 discloses that (it has 76 moles of % propylene contents by allowing liquid polymers, limiting viscosity is 0.03dl/g, Mn is 730, MWD be 1.88 and iodine number be 35) heat the liquid propene-1-Butylene copolymer of prepared a kind of methacrylic acid n-butyl modification with the methacrylic acid n-butyl.

JP-A-01/132605 discloses epoxidised liquid alpha-olefinic polymer, and it is according to disclosed method among the JP-A-63/037102 that is discussed in top last paragraph, prepares from the liquid alpha-olefinic polymer.This epoxy polymer especially can be used as the compatilizer in the lubricating oil composition.

DE-A-4030399 has told about a kind of polymkeric substance and oligopolymer with propylene of end functional groups, it be by contain heteroatomic organic compound with by the another kind of C of propylene and 0-40wt% ₂-C ₈Polymkeric substance that the 1-alkene constitutes and oligopolymer carry out prepared in reaction.The Mn of this polymkeric substance and oligopolymer is 100-100,000, and MWD is 1-3 and a unsaturated end of the chain.Preferably, they are to carry out the polyreaction preparation by monomer in the presence of metallocenes-alumoxane catalyst system at bridge joint.Embodiment 1 discloses by using the isotactic polypropylene oligopolymer of the luxuriant preparation of the zirconium (Mn=800 of silane bridge joint; MWD=2.3) method.The embodiment of back open from embodiment 1 prepared oligomerization of propene thing prepare the method for the oligopolymer of acid anhydrides, mercaptan, epoxide and carboxylic acid terminal.It is compatible containing heteroatomic functionalized polymeric and oligopolymer and polar polymer, and can mix with polar polymer and obtain alloy or multipolymer.

The present invention is directed to the oil-soluble dispersant additive, it comprises (a) and reaction product (b):

(a) after functionalized, in its structure, have at least one and be selected from C ₄-C ₁₀Dicarboxylic acid and its deriveding group and C ₃-C ₁₀A kind of multipolymer of the acyl group functional group of monocarboxylic acid and its deriveding group, this multipolymer comprises from 1-butylene and at least a other having general formula CH ₂Alpha-olefin derived and the next unit of=CHR ', wherein R ' is methyl or C ₃-C ₁₂Linearity or branched-alkyl, this multipolymer have that number-average molecular weight is at least about 700, molecular weight distribution be lower than 5 and with in whole polymer chains at least about 30% end capped vinylidene.

(b) at least a compound of using for derivatization reaction that comprises nucleophilic reactant.

Functionalized multipolymer can be by 1-butylene-alpha-olefin copolymer and single unsaturated C ₄-C ₁₀Dicarboxylic acid reactant compound and single unsaturated C ₃-C ₁₀The monocarboxylic acid reactant compound reacts and prepares.Suitable nucleophilic reactant comprises amine, alcohols, amido alcohols, reactive behavior metallic compound and their mixture.

This dispersant additives has improved viscosity characteristics with respect to corresponding commodity PIB base dispersion agent.More particularly, the having higher molecular weight of the application of the invention and do not influence the dispersant additives of the viscometric properties of system can prepare the oils and the multifunctional additive for lubricating oils of preparation.

Because dispersant additives is based on the multipolymer of the unsaturated position of the end vinylidene with high level, this additive has high activity component concentration, thereby having strengthened the lubricating oil dispersing property, this can be shown by enhanced sludge and lacquer membranoid substance (varnish) control performance.

Fig. 1 is 1-butylene-propylene copolymer and the Mn=2 of embodiment 1, the kinematic viscosity of the S150N mineral oil solution of 225 polyisobutene and the relation curve of strength of solution.

Fig. 2 is 1-butylene-propylene copolymer and the Mn=2 of embodiment 1, the CCS viscosity of the S150N mineral oil solution of 225 polyisobutene and the relation curve of strength of solution.

Fig. 3 is the kinematic viscosity of S150N mineral oil solution of the BPSA/PAM dispersion agent of embodiment 2 and PIBSA/PAM dispersion agent and the relation curve of strength of solution.

Fig. 4 is the CCS viscosity of S150N mineral oil solution of the BPSA/PAM dispersion agent of embodiment 2 and PIBSA/PAM dispersion agent and the relation curve of strength of solution.

The preparation of 1-1-butene-alpha-olefin copolymers

The copolymer that is used for making dispersant additives of the present invention is oil-soluble copolymer, and it contains the unsaturated position of inferior vinyl, end of height and obtains from 1-butylene and at least a alpha-olefin that other has following general formula (I):

             CH ₂=CHR ' (I) wherein R ' be methyl or C₃-C ₁₂Linearity or branched-alkyl. R ' is methyl or C preferably₃-C ₁₀Alkyl and more preferably methyl or C₃-C ₈Alkyl. When alkyl was branching, it was preferably in vinyl bonds and branch Between have at least one-CH₂-group. Most preferably be that R ' group is methyl or has 3-6 carbon former The linear alkyl of son; Be propyl group, normal-butyl, n-pentyl or positive hexyl. Particularly preferably be R ' group It is methyl.

Useful comonomer comprises propylene, 1-amylene, 1-hexene, 1-heptene, 1-octene, 1-ninth of the ten Heavenly Stems Alkene, 1-decene, 1-endecatylene, 1-12 carbenes, 1-13 carbenes, tetradecene, 4-Methyl-1-pentene, 5-methyl isophthalic acid-hexene, 6-methyl isophthalic acid-heptene, 7-methyl isophthalic acid-octene, etc. Excellent The choosing comonomer comprise propylene, 1-hexene and 1-octene, most preferably be propylene. 1-of the present invention Butylene copolymer comprises the copolymer of ternary and Geng Gao, but preferred bipolymer. Therefore, preferred Copolymer comprises 1-butylene-propylene copolymer, 1-butene-1-hexene copolymer and 1-butene-1-Octene copolymer. Most preferably be 1-butylene-propylene copolymer.

Copolymer of the present invention has number-average molecular weight at least about 700, is generally about 700-10,000, be preferably about 1,000-5,000 and most preferably be about 1,500-4,000 (for example 2,000-3.500). This copolymer also has molecular weight distribution, is defined as weight average molecular weight and the equal molecule of number The ratio of amount (is MWD=Mw/ Mn), for being lower than 5, preferably be lower than 4, (for example most preferably be lower than 3 Between 1.1-2.5). Can be measured by gel infiltration chromatography (GPC) by enough suitable caliberators Mw With Mn. GPC measures Mw and The use of Mn for example is described in W.W.Yau, J.J. Kirkland and D.D.Bly, Modern Size Exclusion Liquid Chromatography, John Wiley﹠Sons, New York, 1979.

Butene-1 copolymer of the present invention has the unsaturated position of inferior vinyl, end of height. Therefore, altogether One end of poly-thing has general formula POLY-C (R ")=CH₂, wherein POLY representation polymer chain and R " are C₁-C ₁₂Alkyl. If the 1-butylene is ended chain, R " be ethyl, i.e. C₂Alkyl. In addition, R " The comonomer of determining to depend on selection and the combined polymerization of 1-butylene of alkyl. For example, if selected Comonomer be that propylene and propylene units make polymer chain end-blocking, R " is methyl so. Of the present invention Copolymer contains the inferior vinyl with at least about 30% polymer chain end-blocking. More preferably, inferior second The alkene base will at least 50% polymer chain end-blocking and polymer chain end-blocking (example that most preferably will at least 70% Such as 70-98%). In addition, a small amount of polymer chain contains the unsaturated position of end vinyl (that is, POLY-CH=CH₂, wherein-CH=CH₂Vinyl) and the polymer of a part contain inner single Unsaturated position (for example, POLY-CH=CHR ", wherein R " as defined above). Demonstrate the Asia, end The percentage of the polymer chain of the unsaturated position of vinyl can be by the FTIR spectra methods, titration or by¹³C or proton N MR measure.

Butene-1 copolymer of the present invention comprises any oil-soluble copolymer, this multipolymer contain from 1-butylene derive and the unit that comes with at least some from the comonomer-derived of general formula (I) and the unit, wherein multipolymer has high aforesaid end degree of unsaturation.Yet multipolymer preferably of the present invention contains at least about 5 moles of %, and more preferably at least 10 moles of %'s derives and next unit from alpha-olefin comonomer.Correspondingly, derive and the unitary content that comes preferably is no more than about 95 moles of % and more preferably no more than 90 moles of % from 1-butylene.Especially, 1-butylene-propylene copolymer of the present invention preferably contain the 5 moles of %-40 mole % that have an appointment (for example, 10-40 mole %), more preferably from about 10-35 mole % (for example, 15-35 mole %), most preferably from about 15-30 mole % (for example, 18-25 mole %) is from the next unit of propylene derived.

Being used for multipolymer of the present invention can characterize according to tacticity.The skeleton of alpha-olefin homo and multipolymer is generally formed by replacing methylene radical and methine carbon, and the alkyl side chain that is connected in methine carbon is arranged.Therefore, these polymkeric substance do not resemble PIB, have asymmetric carbon on their polymer backbone, and according to their three-dimensional chemical configuration; Be that tacticity characterizes.In atactic alpha-olefinic polymer, the alkyl side chain on methine carbon has random orientation along polymer backbone.Have to the methine carbon arbitrariness R and S configuration, produce the similar configuration (meso or " m " diploid) or the dissimilar configuration (racemize or " r " diploid) of phase adjacency pair.Atactic polymkeric substance approximately contains identical fractional meso and racemize diploid.Isotactic alpha-olefinic polymer mainly contains the methyne side chain at the same side of polymer backbone or same planar orientation, wherein in chain three kinds of monomeric units (triploid any given sequence can be stated as two successive meso diploids (" mm ").Syndiotactic polymer mainly contains the methyne side chain from a side of polymer backbone to the opposite side sequence alternate, and wherein any given triploid can be stated as two successive racemizes (" rr ") triploid in chain.

In one embodiment of the invention, the butene-1 copolymer that is used for preparing dispersant additives of the present invention can have high isotactic index.Isotactic index is the percentage ratio that isotactic (mm) triploid sequence accounts for the sum of existing triploid sequence in the copolymer chain.Syndiotaxy (rr) and assorted together upright structure (mr) triploid sequence also can exist.By using ¹³C NMR can measure the relative abundance and the isotactic index of triploid sequence.High isotactic index is defined as at least 70% here.Isotactic index be 70%-75% or 80% or the butene-1 copolymer of the general formula (I) of higher (for example 80%-90%) can be incorporated in the dispersant additives of the present invention.

Highly isotactic polymkeric substance is crystal material normally, and it is not suitable for use in the skeleton of dispersant additives, because their limited oil soluble.Highly isotactic poly-1-butylene for example, is higher than at about 1,500 o'clock at Mn and generally has little oil soluble or do not have oil soluble.On the other hand, the isotactic butene-1 copolymer of height that can be used for making dispersant additives of the present invention is unbodied fully, thereby is higher than at Mn and has oil soluble more than 1,500.Side chain is introduced in the unit that comes from the alpha-olefin derived of general formula (I), and the length of this side chain is different from the length of the ethyl side chains of introducing the unit that comes by deriving from 1-butylene.Two kinds of side chains with different chain length along the existence of main polymer chain can disturb and reduce multipolymer degree of crystallinity (promptly improving its amorphous property) and, with respect to similar poly-1-butylene, perhaps give oil soluble or significantly strengthen oil soluble with same polymeric degree.

1-butylene-alpha-olefin copolymer in the present invention can or cooperate in the presence of the catalyst system of product in the reaction that comprises the transistion metal compound (being also referred to as metallocenes) that contains cyclopentadienyl and promotor, carries out polyreaction by the monomer mixture of the alpha-olefin that comprises 1-butylene and general formula (I) and prepares.Metallocenes generally is at Handboook oof Chemistry and Physics (chemistry and physics handbook), the 61st edition, and CRC press, the cyclopentadienyl derivative of disclosed periodic table of elements IVB-VIB group 4 transition metal in 1980.Metallocenes is transformed into active polymerizing catalyst by reacting or combine with promotor, and promotor generally is aikyiaiurnirsoxan beta or ion activation agent, for example ion-exchange compound or lewis acidic negatively charged ion.

The illustrative example of useful metallocenes is to contain those of two cyclopentadienyl ligands by what following general formula was represented: C wherein _pAnd C _p ^*Be identical or different respectively by 0-5 S and S ^*The cyclopentadienyl rings that substituting group replaces, wherein S and S ^*Be independently selected from and C _pThe carbon atom of ring forms those groups of covalent linkage, and comprise alkyl, the substituted hydrocarbon radical that wherein one or more hydrogen are replaced by halogen, the halocarbon base, the IVA family metalloid radicals that alkyl replaces, the IVA family metalloid radicals that the halocarbon base replaces, dibasic boron group, dibasic phosphorus family group, the chalcogen group of replacement, and halogen group.In addition, C _pAnd C _p ^*Be cyclopentadienyl rings, the S of wherein any two vicinities or S ^*Group can be joined together to form C ₄-C ₂₀Ring obtains saturated or unsaturated many ring cyclopentadienyl rings.

A ' is the bridge joint base, and it is used for limiting C _pAnd C _p ^*The rotation of ring; Y is 0 or 1; M is a titanium, zirconium or hafnium; X and X ' are halogen group independently, hydrogen root, alkyl, the substituted hydrocarbon radical that wherein one or more hydrogen atoms are replaced by halogen, the organic quasi-metal group that halocarbon base and alkyl or halocarbon base replace.Perhaps, X and X ' link together and are bonded in atoms metal M, thereby form the metallization ring that contains 3-20 the carbon atom of having an appointment.

Be suitable as S, S ^*, the alkyl of X and X ' and substituted hydrocarbon radical comprise straight chain and branched-chain alkyl and alkenyl (methyl for example, chloromethyl, ethyl, propyl group, propenyl, sec.-propyl etc.), cyclic hydrocarbon group (cyclohexyl for example, brominated hexyl, Deng), the cyclic hydrocarbon group that alkyl replaces, aromatic group (phenyl for example, right-chloro-phenyl-and similar group), the aromatic group that replaces with alkyl (for example tolyl is right-chloromethyl phenyl, etc.).Alkyl and substituted hydrocarbon radical preferably contain 1-20 the carbon atom of having an appointment.

Be suitable as S, S ^*, the halocarbon base class of X and X ' is similar to the alkyl of describing in front the paragraph, and just all hydrogen atoms are replaced by halogen atom.

Be suitable as S, S ^*, that the organic quasi-metal group of X and X ' comprises is single-, two-and the organic quasi-metal group of trisubstituted IVA family element, wherein each alkyl and halocarbon base respectively such as in above two paragraphs definition.The IVA family organic quasi-metal group that suitable alkyl replaces comprises trimethyl silyl, triethylsilyl, triphenyl silyl, ethyl dimetylsilyl, triphenyl germyl, trimethylammonium germyl and similar group.

Be suitable as S, S ^*, the halogen group of X and X ' comprises fluorine, chlorine, bromine and iodine.

Be suitable as S, S ^*Two replace boron groups can be by formula R ^aR ^bB-represents; Two suitable replacement phosphorus belong to group by R ^aR ^bA-represents; With suitable replacement chalcogen group by R ^aG-represents; Wherein B is a boron, and A is a VA family atom, and G is a VIA family atom, and R ^aAnd R ^bBe selected from the hydrogen root independently of each other, the substituted hydrocarbon radical that alkyl and wherein one or more hydrogen are replaced by halogen.Therefore, two suitable replacement boron groups are dialkyl group boryls, the bicyclic alkyl boryl, and the diaryl boryl, two alkaryl boryls, or the like.Two suitable replacement phosphorus belong to group and comprise amino, dialkyl amido, and ammonia diaryl base, bicyclic alkyl amino, phosphino-, the dialkyl group phosphino-, diarylphosphino, the dialkyl group arsyl, or the like.Suitable replacement chalcogen group comprises hydroxyl, alkoxyl group, and cycloalkyloxy, aryloxy, alkoxy aryl, sulfydryl, alkylthio, cycloalkylthio, arylthio, or the like.

S or S by two vicinities ^*The example of saturated or undersaturated many lopps cyclopentadienyl rings that group is connected to form is an indenyl, 4,5,6, and 7-tetrahydro indenyl, fluorenyl, and octahydrofluorenyl.

A ' makes the structurally group of bridge joint of cyclopentadienyl rings ligand.Proper A ' be bivalent hydrocarbon radical, as alkylidene group; For example methylene radical, ethylidene and propylidene.Other proper A ' comprise silicon-containing group, as silicylene (silanylene), silicon alkylidene group, oxygen silicylene and oxygen silicon alkylidene group.

Formula when the metallocenes of bridge joint is not by y=0 (II) expression.

In order to prepare the isotactic butene-1 copolymer that is used for dispersant additives of the present invention, the metallocenes that uses in catalyst system is a chipal compounds, is its pure L or pure D form or their racemic mixture.The metallocenes that is used for preparing the general formula (II) of isotactic butene-1 copolymer is wherein S and S ^*Through meeting the following conditions after selecting those: this metallocenes does not have the symmetrical plane and the symmetrical C that has by metal center at containing metal center ₂Axle.

The illustrative example of bridged metallocents that can be used for producing the general formula (II) of butene-1 copolymer is two (indenyl) zirconium dimethyls of dimethyl-silyl, two (indenyl) zirconium dichlorides of dimetylsilyl, ethylenebis (indenyl) zirconium dimethyl, ethylenebis (indenyl) zirconium dichloride, dimetylsilyl two (4,5,6, the 7-tetrahydro indenyl) zirconium dimethyl, dimetylsilyl two (4,5,6, the 7-tetrahydro indenyl) zirconium dichloride, ethylenebis (4,5,6, the 7-tetrahydro indenyl) zirconium dimethyl, ethylenebis (4,5,6, the 7-tetrahydro indenyl) zirconium dichloride, two (3-methyl cyclopentadienyl) zirconium dimethyls of dimetylsilyl, and ethylenebis (3-methyl cyclopentadienyl) zirconium dichloride, and the luxuriant hafnium analogue of above-mentioned zirconium.Above-mentioned metallocenes can be with their pure L, pure D, and racemize and/or meso-form are used.The racemic form of above-mentioned metallocenes can be produced isotactic polymkeric substance.

Illustrative example by the metallocenes of the not bridge joint of the expression of the general formula of y=0 (II) wherein is the luxuriant class of metal diaikyl, as two (cyclopentadienyl) dimethyl titanium, two (cyclopentadienyl) phenylbenzene titanium, two (cyclopentadienyl) dibenzyl titanium, two (cyclopentadienyl) zirconium dimethyl, two (cyclopentadienyl) phenylbenzene zirconium, with two (cyclopentadienyl) dibenzyl zirconium, and monoalkyl class of metallocenes, as two (cyclopentadienyl) hydrochlorinate zirconium, two (cyclopentadienyl) methyl zirconium chloride and two (cyclopentadienyl) phenyl zirconium chloride.

Illustrative example by the metallocenes of the not bridge joint of the expression of the general formula of y=0 (II) wherein, (they come the rotation of limit collar pentadienyl ligand to obtain tacticity control by the substituting group that enough spatial volumes are arranged on cyclopentadienyl rings, thereby satisfy for producing the necessary symmetric condition of isotactic as mentioned above polymkeric substance), comprise two (three ring [5.2.1.0 ^2,6] last of the ten Heavenly stems-2, the 5-dialkylene) zirconium dimethyl, two ((1R)-9,9-dimethyl three ring [6.1.1.0 ^2,6] last of the ten Heavenly stems-2, the 5-dialkylene) zirconium dimethyl, two (three ring [5.2.1.0 ^2,6] last of the ten Heavenly stems-2,5, the 8-trialkenyl) zirconium dimethyl, two (three ring [5.2.2.0 ^2,6] 11 carbon-2,5, the 8-trialkenyl) zirconium dimethyl, two ((1R, 8R)-7,7,9,9-tetramethyl-[6.1.1.0 ^2,6]-2, the 5-dialkylene) zirconium dimethyl and the luxuriant hafnium analogue of above-mentioned zirconium.

Above-described metallocenes by with general formula (R ^c-Al-O) _pRing-type aikyiaiurnirsoxan beta or general formula R ^c(R ^c-Al-O) _qThe reaction of linear aikyiaiurnirsoxan beta, in conjunction with or cooperate and can be activated into catalysis state, wherein R ^cBe C ₁-C ₅Alkyl (for example methyl, ethyl, propyl group, butyl or amyl group) and p and q are the integers among the 2-about 25.Most preferably, R ^cBe that methyl and p and q are 4 at least.Aikyiaiurnirsoxan beta can prepare described in 153,157 according to US-A-5, and its disclosure is incorporated herein for reference.

The metallocenes of general formula (II), wherein X and X ' are independently selected from hydrogen root, C ₁-C ₂₀Alkyl, the replacement C that one or more hydrogen atoms are replaced by halogen ₁-C ₂₀Alkyl, and C ₁-C ₂₀The IVa family metalloid radicals that alkyl replaces, or wherein X and X ' are connected and are bonded in M and form C ₃-C ₂₀The metallization ring also can be activated by ion activation agent such as ion-exchange compound.Ion-exchange compound generally comprise can with the ligand generation irreversible reaction of metallocenes (for example giving proton) or can be in addition and the positively charged ion that reacts of the non-cyclopentadienyl ligand of metallocenes and with metallocenes cationic-compatible and non-coordinate negatively charged ion by the reaction generation of metallocenes and activator.

The activator compound that contains single anion binding compound can be expressed from the next:

[[L′-H]+] _d[(M′) ^m+Q1Q2…Qn] ^d- (III)

Wherein L ' is a neutral Lewis base, and H is a hydrogen atom, [L '-H] be bronsted acid, M ' is metal or metalloid, and Q1 to Qn is the hydrogen root independently, alkyl and substituted hydrocarbon radical, halocarbon base and replace the halocarbon base, and alkyl-and the organic quasi-metal group that replaces of halocarbon base, dibasic phosphorus belongs to group, among chalcogen group that replaces and the Q1-Qn any one, but being no more than one, can be halogen atom, and m is an integer of representing the form valence state electric charge of M ', n is the sum of ligand Q, and n-m=d.

Any metal or the metalloid that can be formed in anionic complex stable in the water can use or be contained in the negatively charged ion of second kind of compound.Suitable metal comprises aluminium, gold, platinum etc.Suitable metalloid comprises boron, phosphorus, silicon etc.Because commercial sources obtains easily, contain and a kind ofly comprise that the salt of the coordination compound negatively charged ion of (it contains single boron atom) (for example four (pentafluorophenyl group) boron anion) is preferred.The suitable combination thing that contains single boron atom comprises two-or trialkyl ammonium salts, N, N-dialkyl benzene ammonium salt and triaryl microcosmic salt.

The ion activation agent of general formula (III) also can contain a plurality of boron atoms, as carborane, and metallocarborane (metallacarborane), and borine.

Other narration (comprising other embodiment) that contains single negatively charged ion and can be used to activate the luxuriant ion activation agent of chiral metal is provided at EP-A-277003, EP-A-277004, WO-A-92/00333, unexamined, the general USSN852437 (application on March 16th, 1992) that transfers the possession of of Buddhist monk, it is for reference that their disclosure is introduced into this paper.

In addition, ion-exchange compound can contain consistency, non-coordinate polyanion described in WO-A-93/011172, and the content of this patent documentation is incorporated herein for reference.

The metallocenes that is used for producing the butene-1 copolymer that uses in the present invention also can be activated by relative lewis acidity those lewis acidic negatively charged ion more than or equal to the relative lewis acidity of two (perfluorophenyl) borines of phenyl, described in EP-A-520732, it is for reference that its disclosure is introduced into this paper.

Metallocenes-aikyiaiurnirsoxan beta olefin polymerization catalysis in addition can be according to US-A-4,752,597 produce as reaction product, this patent documentation discloses: by at least a metallocenes and the aikyiaiurnirsoxan beta of IVB family metal in the periodic table of elements, according to mol ratio 1: 12-1: 100 (are basic calculation with metal and aluminium) are reacted and are obtained this reaction product of solid.

Contacting the catalyst system that obtains with aikyiaiurnirsoxan beta or ion activation agent by metallocenes can be homogeneous, heterogenetic or carrying, and can before in polymerization reactor, introducing component, form.Homogeneous catalyst can be in reactor be mixed in polymerization solvent by each component and forms.The catalyst system that supports can be by with the absorption of metallocenes and activator be engaged on the catalyst loading material and prepare.Further narration about the catalyst system that supports can be at US-A-5057475, US-A-5017714, co-pending application USSN4683382 (application on October 15th, 1991) with the generality transfer, find among USSN885170 (application on May 18th, 1992) and the USSN926006 (application on August 5th, 1992), it is for reference that these publications are introduced into this paper.

Polyreaction can be carried out according to solution or slurry polymerization.By using the liquid copolymeric monomer reactant, promptly the alpha-olefin of 1-butylene and at least a general formula (I) carries out polyreaction as reaction medium.In addition, also can use polyreaction performance inert hydrocarbon solvent/thinner.Suitable diluent comprises straight chain and side chain hydro carbons (propane for example, Trimethylmethane, butane, pentane, iso-pentane, hexane, heptane, octane waits the mixture with them), ring-type and alicyclic hydro carbons (cyclohexane for example, suberane, methylcyclopentane, methylcyclohexane waits the mixture with them), and aromatic hydrocarbons (benzene for example, toluene, dimethylbenzene waits the mixture with them).

The materials flow that contains the 1-butylene reactant can contain to arbitrariness other C ₄Hydro carbons.Materials flow typically contains and is lower than about 5wt%, preferably is lower than 4wt% and most preferably is lower than the iso-butylene of 3wt%; At least about 12wt%, preferably 30wt% and most preferably total n-butene of 45wt% (being 1-butylene and 2-butylene) at least at least; Be lower than divinyl and normal butane and the Trimethylmethane of about 1wt%.C ₄The iso-butylene of materials flow and 2-butylene component be in the presence of the catalyst system and be nonreactive activity basically under the polymeric reaction condition that adopts as described herein, and resulting like this polymkeric substance is gone up substantially not contain by the polyreaction of 2-butylene and iso-butylene and derived and the unit that comes.

These C ₄Materials flow can comprise the useless C that produces as the by product of making polyisobutene or methyl tertiary butyl ether ₄Materials flow, wherein C ₄Materials flow (being also referred to as raffinate II) contains the iso-butylene that is lower than about 5wt%, 1-butylene and the 2-butylene of about 10-70wt% saturated butanes class and about 15-85wt%.Saturated butanes the same thinner or solvent as reaction mixture with iso-butylene and 2-butylene.General C ₄Materials flow is maintained under the enough pressure, so that at reactor inlet be in liquid form in the reaction mixture at itself under the temperature of reaction.

The alpha-olefin comonomer of 1-butylene and general formula (I), no matter use still to use with solvents/diluents blended liquid form with the neat liquid form, can be used as independent materials flow or supply with polymerization reactor as one premix materials flow, wherein the alpha-olefin content of resulting polymkeric substance especially can be controlled by the following: enter the wt% (based on the monomer gross weight) of the 'alpha '-olefin monomers in the reactor, employed concrete polymeric reaction condition and selected catalyst system.

When using alumoxane activator in catalyst system, the mol ratio of aluminium and transition metal can be at about 0.5-100, in 000 scope, and preferably about 1-2,1-1 in 000 scope and most preferably from about, in 500 scopes, 100-1 for example, 000.When using the ion activation agent, can be about 0.1-10 with activator and metallocenes ratio, preferably about 0.3-3 prepares catalyst system.

Polyreaction generally between about-20 ℃ and 300 ℃, preferably under the temperature between about 0 ℃ and 200 ℃, is for example carried out under the temperature between 30-150 ℃.Above-mentioned catalyst system is suitable for alpha-olefin comonomer polyreaction in very wide pressure range in solution of 1-butylene and general formula (I), and wherein control pressure is liquid phase under selected polymerization temperature to keep thinner and reactant monomer.So polymerization pressure generally is at about 100-300,000kPa (1-3,000 crust), preferred about 200-150,000kPa (2-1,500 cling to) and 400-100 most preferably from about, in the scope of 000kPa (4-1,000 crust), for example at 500-2, in the scope of 500kPa (5-25 crust).

Reaction times is not strict and can be according to changing to several minutes or shorter time several hours or longer time such as the factor of temperature of reaction, reaction pressure etc.Ordinary person in the art can be easily by the optimum reacting time of common experiment acquisition for one group of given reaction parameter.

Polyreaction can be ended by usual way, such as allowing polymerization reaction medium and water, alkali, diluted acid or alcohol (for example methyl alcohol, propyl alcohol, Virahol etc.) contact make catalyst system inactivation and/or cooling or flash distillation by medium.Reclaim the product polymkeric substance by well-known in the art method then and purified.

Polyreaction can be undertaken by intermittence or continuation method.When carrying out intermittent polyreaction, the alpha-olefin comonomer of 1-butylene and general formula (I) (arbitrariness ground is with thinner) can be supplied with suitable reactor or supply with suitable reactor individually with any combination of proper ratio with the form of mixture.When using independent materials flow, monomer can feed intake simultaneously or according to any order.Must be noted that all compositions are exsiccant and are substantially free of O ₂, CO, CO ₂And N-, O-and S-polar compound, wherein reactant generally flow through molecular sieve or other drying appliance before they are introduced into reactor.Subsequently, the catalyzer of premix and activator are supplied to reactor in solvents/diluents, and reaction mixture is stirred the beginning polyreaction simultaneously.In addition, catalyzer and activator can be simultaneously or according to any order supply response device individually.In general, in whole polymerization process, come stirred reaction mixture by stirring or alternate manner.When polymer formation, additional monomer is joined in the reactor.After reaction was finished, unreacted monomer and solvent were flashed or distill and remove (using vacuum if necessary) and discharge polymkeric substance from reactor.

Polyreaction can continuous or semi-continuously be carried out: supply with the catalyzer and the activator of independent materials flow form or be blended in a catalyzer and an activator in the materials flow in reactor, simultaneously with 1-butylene, comonomer and arbitrariness can with can no thinner with any array configuration of independent materials flow or supply response device in a materials flow together, from reactor, discharge unreacted monomer, thinner and polymkeric substance simultaneously, thereby make each composition have the sufficiently long residence time to form the polymkeric substance of desired molecule amount.After discharging from reactor, polymkeric substance separates with reaction mixture.

The preferred method for preparing 1-butylene-alpha-olefin copolymer of the present invention is to use metalloscene catalyst and uses the continuous polymerization method that contains 1-butylene liquid stream (wherein the amount of thinner is the 30wt% at least of materials flow before the alpha-olefin with general formula (I) mixes) that dilutes.Preferable methods is disclosed in the general pending trial U.S. serial number of transferring the possession of, (Docket No.PT-974), day application, title are " using the non-ethylene ' alpha '-olefin homopolymer of metallocene catalyst system and the dilution process of copolymer polymerization reaction ", and it is for reference that its disclosure is introduced into this paper.

The preparation of functionalized polymeric

The functionalized polymeric that is used for preparing dispersant additives of the present invention is by being prepared as follows: will have a certain structure division after 1-Butylene copolymer (the following polymkeric substance that the is called simply) chemical modification in its structure, this structure division contains or comprises that at least one is selected from C ₄-C ₁₀Dicarboxylic acid and its derivative and C ₃-C ₁₀The acyl group functional group of monocarboxylic acid and its derivative.Especially, be suitable for of the present invention with single-or this functionalized base polymer of dicarboxylic acid material comprise the reaction product of polymkeric substance and monounsaturated carboxylic acid reaction thing, this reactant comprises at least a compound that is selected from following material group: (i) single unsaturated C ₄-C ₁₀Dicarboxylic acid, wherein (a) carboxyl is connected in contiguous carbon atom and (b) is close to that at least one is the part of single unsaturated group in the carbon atom; (ii) acid anhydrides or C ₁-C ₅The list of alcohol deutero-(i)-or diester deriv; (iii) single unsaturated C ₃-C ₁₀Monocarboxylic acid, wherein carbon-to-carbon double bond is in the allylic of carboxyl; (iv) C ₁-C ₅Alcohol deutero-monoesters (iii).With polymer reaction after, it is saturated that the two keys of single unsaturated carboxylic acid reactant become.Therefore, for example, become succinyl oxide with the maleic anhydride of polymer reaction, toxilic acid becomes succsinic acid and vinylformic acid becomes propionic acid.

The suitable unsaturated acid material that can be used as functionalized compounds comprises vinylformic acid, methacrylic acid, and toxilic acid, maleic anhydride, fumaric acid, etc.Particularly preferably be undersaturated dicarboxylic acid and their derivative, especially toxilic acid, fumaric acid and maleic anhydride.

Under the normal circumstances, the polymkeric substance of a part does not react with single unsaturated carboxylation reaction thing, and product mixtures contains not functionalized polymkeric substance like this.Not the derivatization reaction that can be used in other with the product mixtures of the unsaturated carboxylation reaction thing reaction of any list with, for example, make dispersion agent.

This polymer product can characterize according to its activeconstituents ratio (A.I.), and this A.I. is to be the weight fraction of the functionalized polymeric of basic calculation with functionalized in the product and not functionalized total polymer.The A.I. of polymkeric substance of the present invention generally is at least 0.50, preferred 0.65-0.99, more preferably 0.75-0.99 and most preferably 0.85-0.99.

This polymkeric substance can be in addition functionalized with single unsaturated carboxylation reaction thing by the whole bag of tricks.It is functionalized that these class methods comprise that halogen is assisted, " ene (alkene) " reaction, and free radical grafting.For the functionalization of polymers that halogen is assisted, at first allow halogen under 60-250 ℃, make polymkeric substance by halogenation about 1-8wt% halogen (for example chlorine or bromine) extremely, based on polymer weight by polymkeric substance through about 0.5-10 hour.The unsaturated carboxylation reaction thing of the list of halogenated polymer and q.s reacted about 0.5-10 hour down at 100-250 ℃ then, and the product of such acquisition like this contains the unsaturated carboxylation reaction thing of list of required mole number for every mole halogenated polymer.These class methods of general type are told about among US-A-3172892 and the US-A-3272746 at US-A-3087936, and it is for reference that these documents are introduced into this paper.In addition, when halogen (for example nitrogen) fed in the hot material, polymkeric substance and single unsaturated carboxylation reaction thing can mixed and heating.The method of this type is disclosed in US-A-3215707, and in 3231587,3912764,4110349 and 4234435 and in UK-A-1440219, it is for reference that their disclosure is introduced into this paper.

Polymkeric substance also can contact at elevated temperatures with single unsaturated carboxylation reaction thing and cause that heat " alkene " takes place reacts.In general, there be not O ₂With under the situation of water (for example at N ₂Following) and under agitation, polymkeric substance and carboxylation reaction thing are about 1: 1 to 10: 1 according to carboxylation reaction thing and polymkeric substance mol ratio, contact is about 1-20 hour under the temperature between about 120-260 ℃.Heat " alkene " method is described among US-A-3361673 and the US-A-3401118, and it is for reference that their disclosure is introduced into this paper.

By using the reaction of heat " alkene (ene) " type or preparing functionalized polymkeric substance according to disclosed chlorination like that in addition among the US-A-5266223 (it is for reference that its disclosure is introduced into this paper).

By using radical initiator (superoxide for example, azo-compounds etc.), single unsaturated carboxylation reaction thing can be grafted on the polymkeric substance of solution or solid form and be formed with the carboxylic acid structure part or the random functionalized polymeric that is distributed in the derived structure part in its structure is arranged.The graft reaction that free radical causes generally under the elevated temperature between about 100-250 ℃, preferably carry out in inert atmosphere by (for example N2 atmosphere).

Derived polymers

By the functionalized polymeric of the above preparation (being carboxylic acid/anhydride/carboxylicesters that polymkeric substance replaces) by with such as nucleophilic reactants such as amine, amido alcohols, alcohols, reactive behavior metal, reactive behavior metallic compounds reaction derive form derived polymers and.Derived polymers composition of the present invention can be as the dispersion agent in lubricant and the fuel composition.

From the amine derived polymers

The aminated compounds of functionalized polymeric of being used for deriving comprises at least one amido and can comprise one or more additional amines or other reactive behavior polar group.The functional group and the amine reaction that comprise carboxylic acid, ester or their deriveding group form acid amides or imide.

Preferred amine is aliphatic saturated amine, is included in to contain the 2-60 that has an appointment in the molecule altogether, and the preferred individual carbon atom of 2-40 (for example 3-20) and about 1-12, the list of preferred 3-12 nitrogen-atoms (for example 3-9 nitrogen-atoms)-and (preferably) polyamines.These amines can be that alkylamine maybe can be to comprise for example alkyl amine of hydroxyl, alkoxyl group, amide group, itrile group, imidazolinyl and similar group of other group.It all is useful especially having the hydroxyl amine (being also referred to as the amido alcohols) of 1-6 hydroxyl and polyethylene polyamine class such as diethylenetriamine, Triethylenetetramine (TETA), tetren and analogue and their mixture.

Useful amine also comprises the alicyclic diamine class, heterocyclic nitrogen compounds such as tetrahydroglyoxaline, the commodity mixture of aminated compounds (for example the per molecule of buying as " PolyamineH ", " Polyamine 400 " etc. with trade(brand)name on average contains the polyethylene polyamine compound of 5-7 nitrogen-atoms), the poly suboxygen alkyl polyamine, with polyamide-based and relevant amine, these are at US-A-4857217, describe in 4963275 and 4956107, and it is for reference that the disclosure of these patent documentations is introduced into this paper.

By allow amine compound with (in inert organic liquid (for example mineral oil) dissolving or be diluted to the concentration of about 5-95wt%) singly-or the in addition functionalized polymkeric substance of the present invention of dicarboxylic acid material (for example succinyl oxide) react and prepare no ash content dispersion agent.This reaction generally under about 100-250 ℃ temperature about 1-10 hour is up to removing till the water of pre-metering.Preferably heating operation helps forming imide or acid amides and imido mixture, rather than acid amides and salt.The relative proportion of functionalized polymeric and amine mainly changes according to the type of reactant and formed key, but in general, for every normal amine, uses the 0.05-1 mole to produce in functionalized polymeric singly-or the structure division content of dicarboxylic acid.

From the alcohols derived polymers

Functionalized polymeric can form the ester class with the alcohols reaction.Alcohols can be the monohydroxy alcohols, poly-hydroxy alcohols, aromatic hydroxy compound, undersaturated alcohols, ether-alcohols or amido alcohols.The poly-hydroxy alcohols is most preferred alcohols and preferably contains 2-10 the hydroxyl of having an appointment.Suitable poly-hydroxy alcohols comprises ethylene glycol, Diethylene Glycol, triethylene glycol, glycerine, tetramethylolmethane or the like.Can allow functionalized for example acid-functionalized polymkeric substance of the present invention and alcohols react according to common esterification techniques.This generally comprises functionalized polymeric is heated with alcohols, arbitrariness ground be generally liquid, basically in the presence of the inert organic liquid solvents/diluents.Can use the temperature that takes place to decompose to one or more reactants at least about 100 ℃.This temperature is usually in about 100-300 ℃ scope and typically in about 140-250 ℃ scope.But esterification arbitrariness ground carries out under esterifying catalyst (for example sulfuric acid, right-toluenesulphonic acids and analogue) exists.

Polymkeric substance from reactive behavior metal/metal compound deriving

Functionalized polymeric of the present invention can form metal-salt or metallic title complex with reactive behavior metal or the reaction of reactive behavior metallic compound.React with reactive behavior metal or metallic compound by functionalized polymeric (be the list that replaces of polymkeric substance-and dicarboxylic acid material) and to form metal-salt.Usually, react by functionalized polymeric and amine as discussed above and/or alcohols reaction and the reactive behavior metallic compound that in amination and/or esterification process or afterwards forms usefulness with title complex and form metal complexes.In general, the compound of basic metal, alkaline-earth metal and transition metal can be used to form metal-salt and title complex.Suitable compound comprises oxide compound, alcoxylates, oxyhydroxide, phenoxy group thing, alkylide (for example methide), nitrate, nitrite, halogenide, carboxylate salt, phosphoric acid salt, phosphite, vitriol, sulphite, carbonate and borate.

Especially, the metal reactant that title complex forms usefulness comprises cadmium and has the metal of atomicity 24-30 (chromium for example, manganese, iron, cobalt, nickel, copper and zinc) nitrate, nitrite, halogenide, carboxylate salt, phosphoric acid salt, phosphite, vitriol, sulphite, carbonate, borate and oxide compound.These metals are so-called transition or coordination metal, and promptly they can form title complex by means of their secondary valency or coordination valence.Can in US-A-3306908, find at the further disclosure that is suitable for forming the reactive behavior metallic compound of this type of title complex and preparing the method for this type of title complex.

Can be used to comprise the oxide compound of basic metal, alkaline-earth metal, zinc, cadmium, lead, cobalt and nickel from the reactive behavior metallic compound that aforesaid functionalized polymeric and/or amine derived polymers prepare salt, oxyhydroxide, carbonate, halogenide, alkylide (for example methide) and phenoxy group thing.Can find US reissue patent 26433 at these reactive behavior metallic compounds with from the further disclosure that they prepare the method for functionalized polymeric salt, it is for reference that its disclosure is introduced into this paper.

Functionalized polymeric can with two or more any mixture reaction in single each amine, alcohol, reactive behavior metal, reactive behavior metallic compound or any of these material.In addition, functionalized polymeric can with amine, alcohols, reactive behavior metal species, reactive behavior metallic compound class, or their mixture simultaneously (walk abreast) or press any consecutive reaction.

Aftertreatment-boronation

Aforesaid amine of the present invention and pure derived polymers can be carried out aftertreatment to be used as dispersion agent, wherein boronating agent is selected from boron oxide, halogenation boron, the ester of boric acid and boric acid, its consumption should be able to provide the used nitrogen of the nitrogen composition of the boron of about 0.1 atomic ratio/every mole to boron/each atomic ratio of about 20 atomic ratios.The derived polymer of boronation can contain about 0.05-2.0wt%, and 0.05-0.7wt% boron for example is based on the gross weight of the nitrogenous compound dispersing agent of this boronation.

Handle and to carry out by the following: add about 0.05-4wt% (based on the weight of derived polymers) boronating agent and under about 100-190 ℃ temperature stirring heating 1-5 hour, carry out the nitrogen extracting subsequently.Preferred boronating agent is a boric acid, and it joins in this nitrogenous compound with slurry form usually.

Lubricating composition

Just as has been noted, derived polymers can be used as the additive in the oily composition, especially dispersant additives.Additive of the present invention is used by being introduced into and being dissolved in oleaginous materials such as fuel and lubricating oil.When additive of the present invention is used for being the oil fuel of liquid under the normal condition, as the middle runnings of boiling range for about 65-430 ℃, comprise kerosene, diesel oil, civilian heating fuel oil, jet fuel etc., usually the concentration of additive in fuel that is adopted is at about 0.001-0.5wt%, in the scope of preferred about 0.005-0.15wt%, based on the gross weight of composition.

Additive of the present invention finds that they are mainly used in lubricating oil composition, and their use has additive to be dissolved in or be scattered in wherein substrate oil.Substrate oil is to have the oils of lubricant viscosity and can is natural oil (for example liquid petroleum) or synthetic oil (for example hydrocarbon ils such as polybutene, the Anaesthetie Ether of the alkylene oxide polymer of terminal groups modification and multipolymer such as polypropylene glycol, polyether ester and analogue) or their mixture.

Additive of the present invention can be introduced in the lubricating oil in any mode easily.They can be scattered in or be dissolved in the oil with desired additives concentration and directly join in the oil.In addition, additive can form enriched material with suitable oil-dissolving solvent and the blending of substrate oil, and enriched material obtains final formulation with the lube base stock blending then.This type of dispersion agent enriched material will contain, based on A.I., and about 10-80wt%, the additive of typically about 20-60wt% and preferably approximately 40-50wt% and typically about 40-80wt%, the substrate oil of preferably approximately 40-60wt% is based on enriched material weight.

Additive of the present invention can mix with the common additives of other type, and each brings into play at least a required effect after selecting.Other additive in the lubricating oil formulation is metallic washing composition/inhibitor, viscosity modifier, wear preventive additive and pour point reducer.Metal detergent/inhibitor generally be alkalescence or one or more organic acid basic metal or the alkaline earth salt or their mixture (for example mixture of Ca and Mg salt) of hyperalkaline, (for example sulfonate, naphthenate, phenates etc.).Viscosity modifier generally is that to have number-average molecular weight be 10 ³-10 ⁶Hydrocarbon polymer or polyester, give dispersiveness or some other performances after being derived to arbitrariness, wear preventive additive is oil soluble zinc dithiophosphate dialkyl ester typically.

When composition, in containing these additives one or more, typically be blended in the substrate oil, its consumption is enough to provide effectively their normal predetermined effect.In this composition, general to account for about 0.1-20wt% of composition total weight, the use of preferably approximately 0.1-6wt% additive of the present invention (for example being used as dispersion agent).

One or more the multifunctional additive for lubricating oils of concentrated solution that comprises in additive of the present invention and these other additives can prepare by additive is joined in the substrate oil, and theme additive wherein of the present invention exists with aforesaid concentrated amount.The set amount of theme additive and other additive generally is about 2.5-90wt%, preferably approximately 15-75wt% and the about additive of 25-60wt% most preferably, and substrate oil is surplus.This enriched material generally promisingly provides desired concn and the additive (when enriched material mixes with the substrate of predetermined amount is oily) of the amount of needs through containing after the preparation in final formulation.

Illustrate in greater detail the present invention in the following embodiments, although be the character of giving an example.

The preparation of embodiment 1-1-butylene-propylene copolymer

Trimethylmethane, 1-butylene (99wt% lowest purity), and propylene (99.9wt% lowest purity) is joined in the auger tank (working capacity=150 pound) as liquid individually under helium pressure, formation has the preceding raw mix of reaction of the liquefaction of following composition, composition is a basic calculation with the gross weight of the mixture that comprises thinner, by the flow measurement that joins each component the auger tank from suitable basin: propylene, 4.6%wt; Trimethylmethane, 60.9wt%; And 1-butylene, 34.5wt%.Mixture is crossed contain activated alumina first group by means of the chlorine Continuous Flow of pressurization then and is handled bed and contain the 3A molecular sieve so that remove the moisture of trace the mixture and second group of polar compound handled bed before reacting before the reaction of liquefaction.Mixture is joined the bottom of 1.2 liters of stirred reactors temperature control, the baffle plate baffling then continuously before the reaction.Setting reactor residence time by input speed is 30 minutes.Reactor pressure remains on the 1700kPa gauge pressure.Temperature of reaction is set in 60 ℃.

Meanwhile, two (4,5,6, the 7-tetrahydro indenyl) ZrCl of racemic dimetylsilyl bridge joint ₂The solution of catalyzer and methylaluminoxane promotor is joined in the reactor separately and continuously.By mixture input speed before regulation and control catalyst solution input speed and the reaction, be set at 2.84 * 10 in catalyst reactor concentration ^-5The Gram-mole/liter.Al: the Zr mol ratio is 1150: 1.In nitrogen atmosphere by being dissolved in the racemize 1 in the toluene, two (4 of 1-dimetylsilyl bridge joint, 5,6, the 7-tetrahydro indenyl) the zirconium dichloride catalyzer joins in 10% solution of methylaluminoxane (MAO, molecular weight=1000, aluminium content=5.93 mole %) in toluene, the toluene that adds other subsequently obtains final solution, and has prepared catalyzer-promotor solution earlier.The toluene of all uses all is the process molecular sieve drying.

Discharge the product materials flow continuously from the top of reactor, with the dilute aqueous soln quenching of alkali, the water flushing removes lixiviating, flow through heat exchanger materials flow is heated up and by be vented to normal atmosphere in addition flash distillation so that from polymer product, remove unreacted monomer and normal butane.

Resulting polymkeric substance have according to surveying and determination Mn be 2,880 and molecular weight distribution be 1.68, use the PIB standard by gel permeation chromatography.The propylene content of polymkeric substance by ¹³C NMR is measured as 20 moles of %.

The preparation of embodiment 2-polyamines dispersion agent

In the Parr autoclave pressure, the 1-butylene-propylene copolymer of 200 gram preparations in embodiment 1 and 8.4 gram maleic anhydrides reacted 4 hours down at 250 ℃.Excessive maleic anhydride is 1-butylene-propylene succinyl oxide (BPSA) of 32.7 in 220 ℃ of following extractings acquisition in 1 hour saponification value with nitrogen.Then, 140 gram BPSA are dissolved in the lubricated substrate oil of 113.6 gram S150N mineral, form solution.Time through 25 minutes under 149 ℃ is added drop-wise to 4.7 gram commodity polyamines in the oil solution of BPSA.This polyamines (PAM) comprises that per molecule has the polyethylene polyamine of average about 6 nitrogen-atoms and average about 10 carbon atoms.Solution is used nitrogen extracting 60 minutes down at 160 ℃ then, obtains a kind of dispersant solution that contains 0.62wt%N.

Embodiment 3-viscosity measurement

Polymkeric substance: the S150N mineral oil solution for preparing the 1-butylene-propylene copolymer of preparation in embodiment 1 with several concentration in the 1-8wt% scope.The similar solution that also prepares polyisobutene (Mn=2,225, Mw=5,000).100 ℃ of kinematic viscosity (centistoke) of using ASTM method No.D445 to record solution, the result is depicted as the function of strength of solution, as shown in fig. 1.Similarly, use ASTM method No.D2602 to record the CCS viscosity (centipoise) of solution down at-20 ℃, and plot figure shown in Figure 2.The kinematic viscosity of 1-butylene-propylene copolymer solution and CCS viscosity are lower than the viscosity of polypropylene under same concentration, although the polymerization degree of 1-butylene-propylene copolymer is significantly less than the polymerization degree of polyisobutene.

Dispersion agent:, make the S150N mineral oil solution of the BPSA-PAM dispersion agent of preparation among the embodiment 2 with several concentration in the 0.5-4wt% scope.By chlorination polyisobutene (Mn=2,225, Mw=5,000) low temperature maleation and also can be prepared to similar solution with the prepared commodity PIBSA-PAM dispersion agent of polyamines that comprises (average about 6 nitrogen-atoms and average about 10 carbon atoms are arranged in the per molecule) polyethylene polyamine subsequently, wherein this method reduces about 10-20% with the number-average molecular weight of polyisobutene skeleton.According to described in the earlier paragraphs like that, measure the kinematic viscosity and the CCS viscosity of solution, and depict the function of concentration as, respectively as shown in Fig. 3 and Fig. 4.The kinematic viscosity of BPSA-PAM and PIBSA-PAM is quite similar, although difference is very big on the molecular weight of polymer backbone.

Embodiment 4-SIB/VIB test

In embodiment 2 performance of the BPSA-PAM dispersion agent of preparation with compare in the performance of the boronation PIBSA-PAM dispersion agent described in the embodiment 3, approach is: test to test the lubricating oil composition that contains the dispersion agent that suppresses sludge and test through VIB through SIB and test the lubricating oil composition that contains the dispersion agent that suppresses to coat with lacquer membranoid substance.In the SIB test, dispersion agent is joined in the transparent upper strata edible vegetable oil that obtains from exhausted (once using taxi) crankcase lubricating oil composition.The exhausted crankcase oil contains the substrate mineral lubricating oils, viscosity modifier, and pour point reducer and zinc dithiophosphate dialkyl wear preventive additive, but itself does not have dispersant additives.This upper strata edible vegetable oil was once separated from (in use forming crankcase oil) oily insoluble sludgy deposits thing, but it still contains oil soluble sludge precursor, and this precursor is trending towards forming the insoluble settling of additional oil under the SIB test conditions after heating.Amount (mg) by dispersion agent-oily blend being heated the several hrs and the sludge that will form in blend in air is compared with the formed amount of blank test thing by the similar processing that only contains oil, measures the effect that dispersion agent suppresses sludge.The SIB value is recorded in 1 (high restraining effect) on 11 (unrestraint effect) standard scale.

In the VIB test, dispersion agent mixes with employed identical test oil in the SIB test.This spontaneously after through one or more test periods, the test period comprises heat absorption, thermal cycling and be exposed to NO, SO ₂And water.Relatively come to determine lacquer membranoid substance restraining effect by the inner wall surface of visual inspection test flask and with the blank test thing that does not have additive.The VIB value is recorded on the scale of 1 (high restraining effect)-11 (not having restraining effect).

SIB and VIB are tested more detailed narration can be at U.S.4, finds in 954,572, and it is for reference that disclosure wherein is introduced into this paper.

Under the activeconstituents of equivalent, BPSA-PAM has SIB value=1.37 and VIB value=4, and the PIBSA-PAM of boronation has 4.26SIB and 5VIB.The result shows that under equal viscosity, the BPSA-PAM dispersion agent is superior to PIB base dispersion agent on performance.

Claims (10)

1, a kind of oil-soluble dispersant additive, it comprises (a) and reaction product (b):

(a) after functionalized, in its structure, have at least one and be selected from C ₄-C ₁₀Dicarboxylic acid and its deriveding group and C ₃-C ₁₀A kind of multipolymer of the acyl group functional group of monocarboxylic acid and its deriveding group, this multipolymer comprises from 1-butylene and at least a other having general formula CH ₂Alpha-olefin derived and the next unit of=CHR ', wherein R ' is methyl or C ₃-C ₁₂Linearity or branched-alkyl, this multipolymer have that number-average molecular weight is at least about 700, molecular weight distribution be lower than 5 and with in whole polymer chains at least about 30% end capped vinylidene.

(b) at least a compound of using for derivatization reaction that comprises nucleophilic reactant.

2, according to the dispersant additives of claim 1, wherein the acyl group functional group derives from the unsaturated carboxylation reaction thing of at least a list, and this reactant is selected from: (i) single unsaturated C ₄-C ₁₀Dicarboxylic acid, wherein (a) carboxyl is connected in contiguous carbon atom and (b) is close to that at least one is the part of single unsaturated group in the carbon atom; (ii) acid anhydrides or C ₁-C ₅The list of alcohol deutero-(i)-or diester deriv; (iii) single unsaturated C ₃-C ₁₀Monocarboxylic acid, wherein carbon-to-carbon double bond is in the allylic of carboxyl; (iv) C ₁-C ₅Alcohol deutero-monoesters (iii).

3, the dispersant additives of claim 2, wherein nucleophilic reactant is to be selected from amine, amido alcohols, alcohols, at least a in the mixture of reactive behavior metallic compound and they.

4, according to the dispersant additives of claim 3, wherein nucleophilic reactant is the amine that contains about 2-60 carbon atom and about 1-12 nitrogen-atoms in the per molecule.

5, according to the dispersant additives of claim 4, wherein amine comprises polyethylene polyamine.

6, according to any one dispersant additives among the claim 3-5, wherein the acyl group functional group is selected from least a in succinyl oxide, succsinic acid and the propionic acid.

7, according to the dispersant additives of claim 1, wherein multipolymer has isotactic index and is at least about 70%.

8, according to the dispersant additives of claim 1, wherein additive obtains a kind of boronation dispersant additives that contains about 0.05-2.0wt% boron after by boronation.

9, the lubricant oil concentrate that contains the dispersant additives product of any one among the claim 1-5 of the 10-80wt% that has an appointment or the 7-8.

10, the lubricating oil composition that contains the dispersant additives product of any one among the claim 1-5 of the 0.1-20wt% that has an appointment or the 7-8.

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